Vicinal glycol borates as textile softeners

ABSTRACT

A textile softening composition containing effective amounts of vicinal glycol borates.

Wixon et all [451 Feb. 1, 197

VlllCllNAlL GLl/(ZQ/IL BORATES AS TEXTIHLE SUFTENERS Inventors: Harold Eugene Wixon, New Brunswick; George Vane Scott, Scotch Plains, both of Assignee: Colgate-Palmolive Company, New York,

Filed: Oct. 29, 1969 Appl. No.: 872,383

US. Cl ..252/8.6, 117/1395 CQ, 260/462,

lint. Cl. ..D06|n 113/20 Field of Search ..252/8.6, 135,138, 89;

Primary Examiner-Leon D. Rosdol Assistant Examiner-Harris A. Pitlick Attorney-Herbert S. Sylvester, Murray M. Grill, Norman Blumenltopf, Ronald S. Cornell, Thomas J. Corum, Richard N. Miller and Robert L. Stone [5 7] ABSTRACT A textile softening composition containing effective amounts of vicinal glycol borates.

7 Claims, No Drawings VIC INAL GLYCOL BORATES AS TEXTILE SOFTENERS The present invention relates to textile cleansing and/or softening compositions containing a vicinal glycol-boric acid complex as the softening agent which is compatible with anionic, cationic and nonionic detergents. v

Softening agents have been used in laundering in order to render fabrics or textiles soft, and the term softening" refers to the handle, hand, touch or feel; this is the tactile impression given by textiles to the hand or body and is of aesthetic and commercial importance. Softening realized with such agents varies with a number of factors including: laundry load weight and composition, types of bleach used if any, detergents used, the initial degree of harshness, type of washing machine, water temperature, etc. The most commonly used softening agents are cationic, such as the quaternary ammonium compounds because of their particular effectiveness. However, aforesaid compounds have the serious disadvantage of causing fabric yellowing which is caused by the deposition of yellow color bodies from the rinse water onto the fabric. Color imparted to textiles laundered with cationic softening agents has been found to be related to the amount of softening given to the textiles. That is, with highly colored water supplies, laundered textiles have a greater degree of yellowness or yellow color when a substantial and effective amount of softening agent is used herewith.

In addition to the aforedescribed yellowing problem, the prior art quaternary softening agents are incompatible with anionic detergents commonly used in laundering because of reaction or interaction therewith, thereby depleting the detergency action in the washing operation as well as forming precipitates which deposit on the washed articles, giving them an undesirable appearance. Consequently, fabric-softening applications have necessarily been conducted separately such as after the washing operation, preferably during the rinsing cycle in the laundering of fabrics.

Accordingly, it is an object of this invention to provide compositions capable of simultaneously cleansing and softening fabrics with a minimal, if any, yellowing normally associated with fabric softening.

Another object of this invention is to provide softening agents which are compatible with anionic, cationic and nonionic detergents.

It has now been found that compositions containing the vicinal glycol borates are effective in softening textiles without yellowing, said borate complexes being compatible with organic surfactants, builder salts, bleaches, brighteners and other ingredients normally found in detergent compositions.

The vicinal glycol borates contemplated by this invention as softening agents are prepared by the reaction of boric acid with a vicinal glycol, including glycerol, erythritol, mannitol, sorbitol, dulcitol, etc. The vicinal glycols utilized in this invention are polyhydric alcohols which contain at least two neighboring hydroxy groups in the cisposition, i.e., on the same side of a plane down through the carbon atoms; and are capable of forming boric esters of the following general struc ture:

Suitable vicinal glycols include polyhydric alcohols containing at least two adjacent hydroxy radicals and having from three to 22 carbon atoms. In particular, the useful polyhydric alcohols include the alkane diols such as ethylene glycol, propane diol, butane diol, pentane diol, hexane diol, dodecane diol, etc.; the octylene glycols; glycerol; polyglycerol; erythritol, mannitol, sorbitol, dulcitol, glucose, etc.

The instant vicinal glycol borates may be prepared in situ, i.e., by the addition of the vicinal glycol and the boric acid separately to the aqueous detergent or softening composition and heating to accelerate the reaction in the formation of a complex borate ester; or may be preprepared and added as such to the aqueous medium useful in the detergency process. These borate esters are waxy or viscous liquid which may be adsorbed on a suitable carrier such as builder salts including the silicates, tripolyphosphates, etc., and subsequently dried to a powder. Other suitable carriers include starches, clays, carboxymethylcellulose and the like. The adsorbed borate esters are water dispersible and may be added to the washing machine during the wash cycle either as a powder or a viscous liquid. The boric ester complex may also be solubilized with suitable alcohol hydrotropes and subsequently added to the wash water.

The following examples are indicative of the significantly enhanced softening action of vicinal glycols by the addition of boric acid. In addition, glycerine and hexaglycerol were changed from nonsofteners to softeners by the addition of boric acid. The effect with glycerine was particularly unexpected because very short chains ordinarily are not tactily perceived on towels.

EXAMPLE I A terry cloth was washed with l7 gallons of tap water at l20 F. to which was added 10 grams of an aqueous'slurry containing 46.7 percent linear tridecylbenzene sulfonate dissolved in warm water and 35 grams powdered sodium tripolyphosphate. The towel was air-dried and evaluated for softness on a scale of l which represents no softness to 10 which represents excellent softness. This towel was given a softness rating of l EXAMPLE 2 A towel was treated in accordance with the procedure of example 1 except that 5 grams of C C vicinal glycol-1,2-(carbon chain distribution0.9% C 1.3% C 30.0% C 32.4% C,,,% 23.2% C 12.2% C having a melting point of 64 C.) was dispersed with the sulfonate in ml. of water at the boiling point prior to their addition to the wash water. This towel was given a softness rating of 5 which is indicative of some softness.

EXAMPLE 3 A towel was treated in accordance with the procedure of example 2 except that 2 grams of boric acid was added to the vicinal glycol and the mixture heated to boiling. An opaque oily layer formed at the surface which congealed into an opaque gellatinous mass upon cooling. The sulfonate slurry was added thereto and this mixture added to the wash water. This towel was given a softness rating of 8 which represents superior softness.

EXAMPLE 4 A towel was treated in accordance with the procedure of example except that 5 grams of glycerine was dispersed with the sulfonate slurry in warm water. The towel treated with this composition received a softness rating of l EXAMPLE 5 A towel was treated as in example 4 except that 5 grams of boric acid was dissolved with the glycerine in 40 ml. of hot water and this mixture added to the wash water with the sulfonate slurry. The towel treated with this composition received the softness rating of S which illustrates that the boric acid changes glycerine from a nonsoftening agent to a softening agent.

EXAMPLE 6 A towel was treated as in example 1 except that 5 grams of boric acid was dissolved in the hot sulfonate slurry prior to the addition to the wash water. This towel exhibited no softness, rating 1.

EXAMPLE 7 A towel was treated as in example l except that 8 grams of hexaglycerol was dispersed with the sulfonate slurry in warm water prior to addition to the wash water. This towel also had a softness rating of l EXAMPLE 8 A towel was treated in accordance with example 7 except that 8 grams of boric acid and glycerol were dissolved in 100 ml. of hot water which was added to the wash water together with the sulfonate slurry. This towel received a softness rating of 5.

The aforementioned examples clearly show that the textile softening activity of vicinal glycols is enhanced by complexing them with boric acid. There was no evidence of textile yellowing in the above examples.

EXAMPLE 9 10% C, C vicinal glycol-1,2-borate was mixed with 90 percent tripolyphosphate in an aqueous medium and the mixture dried to a powder. Sixty grams of this powder were added to 60 liters of wash water containing textiles, The fabric exhibited superior softness.

EXAMPLE 10% C C vicinal glycol-1,2-borate complex and 45 percent isopropanol was mixed with 45 percent water whereby the borate complex is solubilized. Sixty grams of the above solution was added to 60 liters of wash water containing assorted fabrics. The treated fabrics exhibited superior softness with no yellowing.

The vicinal glycol borates are valuable softening agents for textiles and fabrics manufactured from synthetic and natural fibers and blends thereof, inclusive of cellulose, dacron-cotton blend, nylon, wool, cotton, orlon blends and the like. These borate-complexes are stable, water-soluble and/or waterdispersible compounds, capable of imparting the desired degree of softness with a minimal, if any yellowing, when utilized in amounts of 1-20 percent and preferably 2-15 percent by weight of the fabric. The fabric treated with the softening agent is impregnated and coated therewith via the transferrance of the agent from the aqueous medium onto the fabric, the higher dosages being retained on the treated fabrics even after several subsequent washings without treatment to yield a soft, fluffy fabric. Laboratory tests have shown fabrics treated in accordance with this invention will not yellow with age or with repeated treatment. Another beneficial characteristics of these softening agents is their compatibility with anionic, cationic and nonionic detergents, thereby enabling their conjoint use to simultaneously effect cleansing and softening.

Fabric softening composition compounds of the instant invention may be employed either alone or in direct combination with conventional detergents. The useful detergents which may be used in conjunction with the instant fabric softening composition include anionic detergents such as alkylbenzene-sulfonic acid and its salts, and compounds of the formula alkyl-phenyl-SO -M, wherein alkyl is an alkyl radical ofa fatty acid and M is hydrogen or an alkali metal, which compounds comprise a well-known class of anionic detergents and include sodium dodecylbenzene sulfonate, potassium dodecylbenzenesulfonate, sodium laurylbenzenesulfonate, sodium cetylbenzenesulfonate. Others are the alkali metal salts of the higher alkylsulfonic acids and the alkali metal dialkyl sulfosuccinates, e.g., sodium dioctylsulfosuccinate, and sodium dihexylsulfosuccinate, sodium sulfoethylphthalate, sodium oleyl-panisidinesulfonate; sodium sodium tetradecanesulfonate; sodium diisopropylnaphthalenesulfonate; sodium octylphenoxyethoxyethylsulsonate, etc.; and the alkali metal alkyl sulfates, e.g., sodium lauryl sulfate.

Among the above-noted alkylbenzene-sulfonic acid and salts thereof, there are included those which are biodegradable and which are particularly characterized by a linear alkyl substituent of from C to C and preferably from C to C It is, of course, understood that the carbon chain length represents, in general, an average chain length since the method for producing such products usually employ alkylating reagents of mixed chain length. It is clear, however, that substantially pure olefins as well as alkylating compounds used in other techniques can and do give alkylated benzene sulfonates wherein the alkyl moiety is substantially (i.e., at least 99 percent) of one chain length, i.'e., C C C or C The linear alkyl benzene sulfonates are further characterized by the position of the benzene ring in the linear alkyl chain, with any of the position isomers (i.e., alpha to omega) being operable and contemplated.

The linear alkyl benzene sulfonates are generally and conveniently prepared by sulfonating the corresponding alkyl benzene hydrocarbons which in turn may be prepared by alkylating benzene with a linear alkyl halide, a l-alkene or a linear primary of secondary alcohol. Pure isomers (of the lphenyl isomer) are prepared by reduction of the acylated benzene (alkyl phenyl ketone) using a modification of the Wolff-Kishner reaction. The 2-phenyl isomer is obtained from n-undecyl phenyl ketone and methyl magnesium bromide to form the tertiary alcohol which is dehydrated to the alkene and then hydrogenated. The S-phenyl isomer is obtained similarly from n-heptyl phenyl ketone and n-butyl magnesium bromide. The other isomers are obtained in a similar manner from the appropriate n-alkyl phenyl ketone and n-alkyl magnesium bromide.

in addition to the benzene sulfonates one may also employ the lower alkyl (C, to C analogs of benzene such as toluene, xylene, the trimethyl benzenes, ethylbenzene, isopropyl benzene and the like. The sulfonates are generally employed in the water soluble salt form which include as the cation, the alkali metals, ammonium, and lower amine and alkanolamine.

Examples of suitable linear alkyl benzene sulfonates:

sodium n-decyl benzene sulfonate sodium n-dodecyl benzene sulfonate sodium n-tetradecyl benzene sulfonate sodium n-pentadecyl benzene sulfonate sodium n-hexadecyl benzene sulfonate and the corresponding lower alkyl substituted homologues of benzene as well as the salts of the cations previously referred to. Mixtures of these sulfonates may, of course, also be used with mixtures which may include compounds wherein the linear alkyl chain is smaller or larger than indicated herein provided that the average chain length in the mixture conforms to the specific requirements of C to C The linear paraffin sulfonates are also a well-known group of compounds and include water soluble salts (alkali metal, amine, alkanolamine, and ammonium) of:

l-decane sulfonic acid l-dodecane sulfonic acid l-tridecane sulfonic acid l-tetradecane sulfonic acid l-pentadecane sulfonic acid l-hexadecane sulfonic acid as well as the other position isomers of the sulfonic acid group.

in addition to the paraffin sulfonates illustrated above, others with the general range ofC to C alkyls may be used, with the most preferable range being from C to C The linear alkyl sulfates which are contemplated in this invention comprise the range of C to C Specific examples include sodium n-decyl sulfate; sodium n-dodecyl sulfate; sodium n-hexadecyl sulfate; sodium n-heptadecyl sulfate; sodium n-octadecyl sulfate; and the ethoxylated (l to I00 moles ethylene oxide) derivatives; and, of course, the other watersoluble salt-forming cations mentioned above.

Also useful in conjunction with the instant invention are nonionic detergents such as alkaryl polyglycol detergents such as alkyl-phenol-ethylene oxide condensates (2-200 moles ethylene oxide), e.g., p-isooctyl phenol-polyethylene oxide (10 ethylene oxide units), long chain alcohol ethylene oxide condensation products (2-200 moles ethylene oxide), e.g.,

dodecyl alcohol-polyethylene oxides having 4 to l6 ethylene oxide units per molecule, polyglyceroi monolaurate, glycol dioleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquioleate, the condensation products of ethylene oxide with sorbitan esters of long chain fatty acids (Tweens), alkylolamides, amine oxides, phosphine oxides, etc.

In addition to the anionic and nonionic detergents which may be employed in conjunction with the instant invention, cationic, ampholytic, and zwitterionic compounds have also been found to be useful. Representative of these compounds which may be employed in conjunction with the instant fabric softening compounds include quaternary ammonium compounds, e.g., distearyl dimethyl ammonium chloride, cetyl trimethyl ammonium bromide, sodium 3-dodecylamino propionate, fatty carbamides, etc.

The composition of the instant invention may also include, in addition to the fabric softening compounds and conventional anionic, cationic, and nonionic detergent compositions, builders, brighteners, germicides, soil suspending agents, antiredeposition agents, antioxidants, bleaches, coloring materials (dyes and pigments), perfumes, water-soluble alcohols, nondetergent alkali metal benzene sulfonates, etc.

The builder is, generally, a water-soluble, inorganic salt which may be a neutral salt, e.g., sodium sulfate or an alkaline builder salt such as phosphates, silicates, bicarbonates, carbonates, and borates. The preferred builders are those characterized as condensed phosphates such as polyphosphates and pyrophosphates. Specific examples of alkaline salts are: tetrasodium, pyrophosphate, pentasodium, tripolyphosphate (either Phase 1 or Phase ll), sodium hexametaphosphate, and the corresponding potassium salts of these compounds, sodium and potassium silicates, e.g., sodium metasilicate and alkaline silicates (Na O; 2Si0 and Na O; 3SiO sodium carbonate, potassium carbonate and sodium and potassium bicarbonate. Other salts may also be used where the compounds are water-soluble. These include the general class of alkali metals, alkaline earth metals, amine, alkanolamine, and ammonium. Other builders which are salts of organic acids may also be used, and in particular the water soluble (alkali metal, ammonium substituted ammonium and amine) salts of aminopolycarboxylic acids such as:

ethylene diamine tetra-acetic acid nitrilo triacetic acid diethylene triamine penta-acetic acid N-( Z-hydroxyethyl) -ethylene diamine triacetic acid lhydroxyethyl-iminodiacetic acid l,2-diaminocyclohexane diacetic acid, and the like.

The vicinal glycol borates defined herein have potential application also in shampoos for hair conditioning, in light duty liquids as hand care ingredients, in hair rinses, in hair sprays, in wash-and-wax products for floors, in furniture preparation, in water-proofing preparations, in textile mill applications such as softener in permanent press garments and in hand lotions.

The new compositions can be packed in paper, plastic or any other suitable packaging medium. For example, said softener and detergent-softener composition can be packaged in a water-soluble plastic material such as polyvinyl alcohol as a premeasured packet for dissolution in the washing machine. The instant formulations can be solid in form, in the character of free-flowing powders, chips, flakes, granules, tablets, soapbars and the like or in the form ofa solution or dispersion.

Although the present invention has been described with reference to particular embodiments and examples, it with be apparent to those skilled in the art that variations and modifications of this invention can be made and that equivalents can be substituted therefore without departing from the principles and true spirit of the invention.

We claim:

1. A textile cleansing or softening composition consisting essentially of a water-soluble organic detergent selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic detergents and an effective softening amount of a cis, vicinal C to C polyhydric alcolhol borate.

2. The composition of claim 1 which contains water-soluble inorganic phosphate builder salt.

3. The composition of claim 1 wherein the organic detergent is an anionic, sulfonate or sulfate.

4. A method for softening fabric which comprises treating said fabric with an aqueous composition containing a cis, vicinal C to C polyhydric alcohol borate, said borate being used in amounts ranging from 1-20 percent by weight of said fabric.

5. A process according to claim 4 wherein said treating is carried out in the presence of a water-soluble organic deter gent selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic detergents.

6. A process according to claim 5 wherein said treating is carried out in the presence of a water-soluble inorganic phosphate builder salt.

7. A process according to claim 6 wherein said polyhydric alcohol borate is a cis, vicinal C, C, glycol borate, said detergent is a linear tridecylbenzene sulfonate and said builder salt is sodium tripolyphosphate. 

2. The composition of claim 1 which contains water-soluble inorganic phosphate builder salt.
 3. The composition of claim 1 wherein the organic detergent is an anionic, sulfonate or sulfate.
 4. A method for softening fabric which comprises treating said fabric with an aqueous composition containing a cis, vicinal C3 to C22 polyhydric alcohol borate, said borate being used in amounts ranging from 1-20 percent by weight of said fabric.
 5. A process according to claim 4 wherein said treating is carried out in the presence of a water-soluble organic detergent selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic detergents.
 6. A process according to claim 5 wherein said treating is carried out in the presence of a water-soluble inorganic phosphate builder salt.
 7. A process according to claim 6 wherein said polyhydric alcohol borate is a cis, vicinal C15-C18 glycol borate, said detergent is a linear tridecylbenzene sulfonate and said builder salt is sodium tripolyphosphate. 